Method of destroying growing weeds



United States Patent )fifice 3,138,446 Patented June 23, 1964 3,138,446METHOD OF DESTROYING GROWING WEEDS Sidney Richter, Chicago, 111.,assignor to Velsicol Chemical Corporation, Chicago, 111., a corporationof Illinois No Drawing. Original application Oct. 13, 1958, Ser. No.766,660, now Patent No. 3,013,056, dated Dec. 12, 1961. Divided and thisapplication Nov. 28, 1961, Ser. No. 155,454

12 Claims. (Cl. 712.6)

This invention relates to new herbicidal compositions of matter. Morespecifically this invention relates to the control of undesirable plantlife with 3-methoxy-2,6-dichlorophenylacetic acid, its anhydride, itsamides, its esters, its alkali metal salts, or its amine salts.3-methoxy-2,6-dichlorophenylacetic acid, which has the structure CHzC OOH will hereinafter be referred to as compound I. This chemical compoundand its derivatives as cited above have marked activity as herbicidesuseful for the control of undesirable plant life.

Compound I can be prepared readily, for example, from the known compound2,6-dichloro-m-cresol. The free hydroxy group in the cresol is firstprotected against reaction in subsequent steps in the synthesis by theaddition of such groups as -CO H, COR (where R=alkyl), PO H and thelike. Thus the protective group can be made the acetyl radical bytreating 2,6-dich1oro-mcresol with acetic anhydride in the presence of afew drops of sulfuric acid as catalyst, or the protective group can bemade the phosphate radical by treating the cresol with POCl With thehydroxy group suitably protected, the 2,6-dichloro-m-cresol ischlorinated to introduce a single chlorine atom into the methyl group.The chlorination, which can be effected with gaseous chlorine, iscatalyzed by light and free radical initiators and is continued until aslight excess of chlorine over the amount theoretically required for theaddition of one gram atom of chlorine into each mole of startingcompound has been added. The chlorination can be carried out merely bypassing chlorine into the molten starting material, but inert solventsor diluents such as carbon tetrachloride can also be used attemperatures up to about reflux temperature.

The 2,4-dichloro-3-chloromethylphenyl acetate is then placed in asuitable solvent or diluent such as methanol and is heated with anaquesous solution of a cyanide such as sodium cyanide to convert it tothe corresponding 2,4-dichloro-3-cyanomethylphenyl acetate. The cyanocompound is hydrolyzed with strong sulfuric acid, for example, inaqueous medium to give the free 2,6-dichloro-3- hydroxyphenylaceticacid. The acid is converted to its alkali metal salt with an alkalimetal hydroxide such as sodium or potassium hydroxide, and the salt isrefluxed in aqueous solution with an excess of dimethyl sulfate. Thereaction mixture is refluxed with additional alkali metal hydroxide tohydrolyze any carboxylic acid ester which may have formed, cooled, andacidified with a mineral acid such as hydrochloric acid. Theprecipitated acid can be filtered off and dried to give a product whichis suitable for many herbicidal uses as such. However, if desired, itcan be purified by crystallization from a suitable solvent. 7

The anhydride of compound I is prepared by the removal of one moleculeof water from two molecules of compound I as the free acid. In practice,it is convenient to prepare the anhydride by the acylation of the freecarboxylic acid by its acid halide in the presence of a strong acylatingagent such as pyridine. Thus, a mixture of dry pyridine and dry benzeneare treated with 1 mole of the acid chloride of compound I. The slightlyexothermic reaction proceeds with the formation of an intermediatepyridinium salt. One mole of compound I as the free acid is then added,the precipitate of pyridine hydrochloride is removed, and the anhydrideof compound I is isolated by removal of the benzene.

The acid halide of compound I required in the above and other synthesesis prepared by the reaction of the free acid with a phosphorus trihalidein the conventional manner. Thus the treatment of compound I withphosphorus trichloride until the reaction ceases produces the acidchloride of compound I.

Compounds which are salts, esters, or amides of compound I can beprepared readily from the free acid. Thus treatment of the free acidwith ammonium hydroxide gives a product which is the salt ammonium3-methoxy-2,6-dichlorophenylacetate. Similarly, an alkali metal salt ofcompound I can be made by the treatment of the free acid with bases,such as the hydroxides, of alkali metals. Treatment of the acid withsodium hydroxide thus gives the salt sodium3-methoXy-2,6-dichlorophenylacetate as the product, While the use ofpotassium hydroxide gives the salt potassium3-methoxy-2,6-dichlorophenylacetate.

Amine salts of compound I are prepared by the addi-v tion of the freeacid to various amines. Typical amines which can be used to prepare suchamine salts are dimethylarnine, trimethylamine, triethylamine,diethanol- 1 amine, triethanolamine, isopropylamine, morpholine, and

the like. The resulting products are, respectively, the dimethylamine,trimethylamine, triethylamine, diethanolamine, triethanolamine,isopropylamine, and morpholine salts of3-methoxy-2,'6-dichlorophenylacetic acid.

Esters of compound I are prepared by the condensation of the acid withvarious alcohols. Thus the condensation of methyl alcohol with compoundI gives the desired ester, methyl 3-methoxy-2,6-dichlorophenylace tate.Other typical alcohols which can be used are propyl, isopropyl, n-butyl,secrbutyl, isobutyl, tert-butyl, amyl, hexyl, heptyl, octyl, nonyl,decyl, and the like. The products are the corresponding alkyl esters of3-methoxy- 2,6-dichlorophenylacetic acid. Although such complex estersas those prepared by the esterification of compound I withbutoxyethanol, propylene glycol butyl ether, and the like are usefulproducts in accordance with this invention, preferred esters are thosein which the esterifying group is an unsubstituted alkyl group whichcontains from 1 to 10 carbon atoms. The condensation of the acid withthe alcohol is carried out suitably in an inert solvent such as anaromatic hydrocarbon and in the presence of a few percent by weight ofan acid catalyst such as p-toluenesulfonic acid. The water which formsduring the esterification reaction can be removed continuously in manycases from the reaction mixture by distillation as it forms, and itsvolume can be measured to determine when the esterification is complete.The ester is then isolated by distillation of the inert solvent. 7

Amides of compound I can be prepared conveniently by the reaction of theacid halide of compound I with ammonia or various amines. The reactioncan be carried out in an inert solvent such as ether or benzene.Preferably two moles of the amine are used for each mole of the acidhalide employed, since the hydrogen halide released during the reactionis taken up by some of the free amine which remains. The simplest amide,Ir-methoxy-2,6-dichlorophenylacetamide, can be prepared by thereaction'of the acid chloride of compound I with ammonia, either as thefree gas or as an aqueous solution. This amide can also be prepared byhydrolysis ofthe corresponding nitrile. Substituted amides are preparedby the reaction of the acid halide of compound I with amines such as anyof the primary or secondary amines suggested above for the preparationof the amine salts of compound I. Thus, for example, the reaction of theacid chloride of compound I with methylamine, butylamine, decylamine, ordiethylamine gives the N-methyl-, N- butyl-, N-decyl-, orN,N-diethyl-3-methoxy-2,6-dichlorophenylacetamides, respectively. Whilemore complex amines such as the aromatic amines can be used as the aminereactant to give desirable products, which are specifically named asanilides, preferred amine reactants are alkylamines containing up to 10carbon atoms.

For practical use as herbicides, the compounds of this invention areformulated with inert carriers to obtain proper concentrations and tofacilitate handling. For example, these compounds can be formulated intodusts by combining them with such inert substances as talc or clays. Thealkali metal salts of compound I are particularly suited to such dustformulations, and dusts containing from 5 to 25 percent by weight ofactive compound are convenient for use in the field. The compounds ofthis invention, however, are preferably applied as sprays. These can bemade as simple solutions by dissolving the compounds in organic solventssuch as xylene, kerosene, or the methylated naphthalenes. The esters ofcompound I, which ordinarily are liquids at room temperature, areparticularly suited to formulation by this method. The amine salts ofcompound I often show good solubility in water and can be used directlyas aqueous solutions.

The compounds of this invention can also be emulsified or suspended inwater by the addition of emulsifiers and wetting agents. Theformulations of these active herbicidal compounds are either applieddirectly to the plants to be controlled, or the soil in which the plantsare growing can be treated. Substances such as other pesticides,stabilizers, activators, synergists, spreaders and adhesives can beadded to the formulations if desired. There is no significant differencein effect from the amount of water or organic solvent for diluting theseherbicides, providing the same amount of chemical is distributed evenlyover a given area. Such distribution can be obtained, for example, withlow-pressure, low-volume sprays at the rate of about gallons of sprayper .acre.

In applying the herbicidal compounds, consideration must be given to thenature and stage of growth of the crop, the species of weeds present,the stage of growth of the weeds, environmental factors influencing therate and vigor of the weed growth, weather conditions at the time ofapplication and immediately following, and the dosage to be applied to agiven area. Weeds are most susceptible when they are small and growingrapidly. Early application, therefore, results in better control withless chemical and increased yields because of the early destruction ofthe competing weeds. The larger and older the weeds the higher theconcentration needed to kill them. Summer annuals such aslambs-quarters, pigweeds, cocklebur, and sunflower should be sprayedwhen they are less than 4 inches high. Winter annuals such as variousmustards, fan-weed, yellow star-thistle, and wild radish are most easilykilled while they are still in the rosette stage. Usually weeds growingrapidly under optimum conditions are relatively susceptible, whereasthose growing under adverse conditions tend to be resistant to theherbicide sprays.

The effectiveness of the compounds of this invention in small quantitiesmakes them economically sound for Weed control on large areas, with agreat saving in labor and cost, in addition to corresponding cropincreases. These compounds are particularly valuable in weed controlbecause they are harmful to many weeds but harmless or relativelyharmless to some cultivated crops. Minute quantities in contact withplant tissues may be absorbed and translocated to all parts of theplant, causing striking changes in the form and functions and oftenresulting in their death. The actual amount of compound to be useddepends on a variety of factors but is influenced primarily by thespecies of undesirable plant to be controlled. Thus while fractions of apound of actual compound I or its equivalent of an ester, salt, amide,or the anhydride of compound I are often sutficient for postemergenceweed control on an acre of corn, seed flax, perennial grass seed crops,pastures or grazing areas (without legumes), wheat, and the like, theparticular species of weeds encountered in evergreen and deciduousdormant nursery stock, nursery conifers, waste areas, woody brush, andthe like may require the use of one or more pounds of compound I or itsderivatives per acre for good control. Dosage adjustments with thelowvolume, low-pressure applications suggested can be made by changingthe nozzle size, nozzle spacing, pressure, or traveling rate of thespray equipment.

The manner in which the herbicidal compounds of this invention can beprepared and utilized is illustrated in the following examples:

EXAMPLE 1 Preparation of 2,6-Dichloro-3-Hydr0xypherzylacetic Acid2,6-dichloro-m-cresol (100 g.; 0.56 mole), which can be obtained, forexample, as described by Huston and Chen in the Journal of the AmericanChemical Society, vol. 55, p. 4217 (1933), is placed with aceticanhydride g.; 0.78 mole) and a few drops of concentrated sulfuric acidin a 250 ml., 3-necked, round-bottomed flask fitted with a mechanicalstirrer, reflux condenser, and internal thermometer. The mixture isstirred and heated at C. for 4 hrs. and is then allowed to stand at roomtemperature overnight. The mixture is then poured slowly with stirringinto a solution of g. sodium bicarbonate in 700 ml. of water and is thenextracted with two 500 ml. portions of ether. The ether extracts arecombined, washed with two 250 ml. portions of 10% sodium hydroxide andthen with two 250 ml. portions of water, dried over magnesium sulfate,and filtered. The ether is distilled off, and the residue is distilledin vacuo to give 2,4-dichloro-3-methylphenyl acetate. The acetate (108g.; 0.49 mole) is placed in a 250 ml., 3-necked, roundbottomed flaskfitted with a mechanical stirrer, reflux condenser, internalthermometer, and gas inlet tube. The acetate is heated and stirred at180 C. while gaseous chlorine is passed into the mixture until 15.6 g.of chlorine has been introduced. The reaction mixture is then cooled togive the desired 2,4-dichloro-3-chloromethylphenyl acetate.

Sodium cyanide (77 g.; 1.57 moles), 110 ml. water, and ml. methanol areplaced in a 1-liter, S-necked, round-bottomed flask fitted with amechanical stirrer and reflux condenser. The mixture is stirred andheated to reflux, and 2,4-dichloro-3-chloromethylphenyl acetate (0.90mole) is added slowly. The mixture is stirred and refluxed for 3 hours,cooled, and extracted with three 300 ml. portions of ether. The combinedether extracts are washed with water, dried over magnesium sulfate, andfiltered. Distillation of the ether gives a residue of2,4-dichloro-3-cyanomethylphenyl acetate. A portion of the cyanocompound (0.80 mole) is stirred and refluxed for 6 hours with 900 ml. ofwater and 750 ml. of concentrated sulfuric acid in a -3-liter, 3-neckedround-bottomed flask with a reflux condenser and a mechanical stirrer.The mixture is then cooled and poured slowly with stirring into 3 litersof ice water. The solid is filtered, washed with cold water, presseddry, and dried completely in a vacuum oven to give2,6-dichloro-3-hydroxyphenylacetic acid.

EXAMPLE 2 Preparation of 3-Methaxy-2,6-Dichlorophenylacetic Acid(Compound I) 2,6-dichloro-3-hydroxyphenylacetic acid (0.87 mole) isdissolved in a solution of sodium hydroxide (139 g.; 3.48

moles) in 900 ml. of water in a 3-liter, round-bottomed flask fittedwith a mechanical stirrer, reflux condenser, dropping funnel, andinternal thermometer. The solution is cooled to- 20 C. and dimethylsulfate (219 g.; 1.74 moles) is added to the vigorously stirredsolution. The mixture is stirred for 20 minutes while the temperature ismaintained below 35 C. by ice-cooling. Another portion of dimethylsulfate (139 g.) is added, and the mixture is stirred for minutes whilethe temperature is maintained below 45 C. The mixture is then refluxedfor 2 hours, treated with a solution of 69.6 g. (1.74 moles) of sodiumhydroxide in 250 ml. of water, and refluxed for an additional 2 hours.The cooled reaction mixture is then acidified to Congo red withhydrochloric acid. The precipitated solid is filtered, dissolved inether, and dried over magnesium sulfate. The ether solution is filtered,and the ether is distilled off to give a residue of the desired compoundI.

EXAMPLE 3 Preparation of the Sodium Salt of Compound I Compound I (0.5mole) is dissolved in 500 cc. of methanol and treated with a solution ofsodium hydroxide (20 g.; 0.5 mole) in 100 cc. of methanol. The methanolis removed by distillation in vacuo on the steam bath, and the solidresidue is slurried with 100 cc. of cold, dry ether, filtered, presseddry, and dried completely in a vacuum oven to give the desired sodiumsalt of compound I.

EXAMPLE 4 Preparation of the Ammonium Salt of Compound I Treatment ofcompound I (0.5 mole) in 500 cc. of methanol with 34 cc. of commercialconcentrated ammonium hydroxide according to the method given in theprevious example gives the desired ammonium salt of compound I.

EXAMPLE 5 Preparation of the Dimethylamine Salt of Compound I Compound I(0.5 mole) is dissolved in 500 cc. of dry ether and treated withdimethylamine (22.5 g.; 0.5 mole). The solid which separates isfiltered, Washed twice with 100 cc. portions of cold ether, filtered,pressed dry, and dried completely in a vacuum oven to give the desireddimethylamine salt of compound I.

EXAMPLE 6 Preparation of the Diethanolamine Salt of Compound I In themanner described in the previous example, compound I (0.5 mole) istreated with diethanolamine (52.5 g.; 0.5 mole) in 500 cc. of dry ether.The product which is isolated is the diethanolamine salt of compound I.

EXAMPLE 7 Preparation of the Morpholine Salt of Compound I Compound I(0.5 mole) is treated with morpholine (43.5 g.; 0.5 mole) in 500 cc. ofether, and the product is Worked up as described for the preparation ofthe dimethylamine salt to give the desired morpholine salt of compoundI.

EXAMPLE 8 Preparation of the Ethyl Ester of Compound I Compound I (0.5mole), ethyl alcohol (23 g.; 0.5 mole), and 3.0 g. of p-toluenesulfonicacid are dissolved in 500 ml. of benzene, and the solution is placed ina 1-liter, round-bottomed flask fitted with a reflux condenser and acalibrated Dean-Stark tube. The solution is heated at reflux temperatureuntil 9 cc. of water have been collected in the Dean-Stark tube. Thecooled reaction mixture is then extracted twice with 50-cc. portions of10% sodium carbonate solution, and filtered. The benzene is distilledoff in vacuo on the steam bath, and

the residue is then distilled in vacuo to give the desired ethyl esterof compound I.

EXAMPLE 9 Preparation of the Decyl Ester of Compound I In the manner andapparatus described in the previous example, compound I (0.5 mole) andnormal primary decyl alcohol (79 g.; 0.5 mole) are refluxed in 500 ml.of benzene in the presence of 3.0 g. of p-toluenesulfonic acid until 9cc. of water have been distilled from the reaction mixture. Work-up ofthe reaction mixture as described in the previous example gives thedesired decyl ester of compound I.

EXAMPLE 10 Preparation of the n-Butyl Ester of Compound I The reactionof compound I (0.5 mole) and n-butyl alcohol (37 g.; 0.5 mole) by themethod described above for the preparation of the ethyl ester is used toprepare the n-butyl ester of compound 1.

EXAMPLE 11 Preparation of the Acid Chloride of Compound I Compound I (1mole) is placed with 500 cc. of dry benzene in a 2-liter,3-necked,'round-bottomed flask fitted with a mechanical stirrer, refluxcondenser (calcium chloride tube), and dropping funnel. Phosphorustrichloride (123 g.; 0.9 mole) is added slowly dropwise with vigorousstirring while the reaction flask is cooled with cold water if necessaryto control the reaction. When all the PCI;; has been added and theevolution of hydrogen chloride has ceased, the reaction mixture is thentransferred to distillation apparatus, and the solvent is'distilled off.The residue is then distilled in vacuo to give the desired acid chlorideof compound I.

EXAMPLE 12 Preparation of the Amide of Compound I One mole of the acidchloride of compound I is placed with 500 cc. of dry benzene in al-liter, 3-necked flask fitted with a reflux condenser, mechanicalstirrer, and a gas inlet tube having a sparger tip. The mixture isstirred while dry ammonia gas is passed into the mixture for severalhours. When the ammonia gas is no longer taken up, the precipitated saltis filtered off and extracted twice with ml. portions of ether. Theether extracts and benzene filtrate are dried over magnesium sulfate andfiltered, and the solvents are distilled off to give the desired amideof compound I.

EXAMPLE 13 Preparation of the N-n-Decylamide of Compound 1 One mole ofthe acid chloride of compound I and 500 ml. of dry benzene are placed ina 2-liter, 3-necked, roundbottom flask fitted with a mechanical stirrer,reflux con- EXAMPLE 14 Preparation of the N,N-Diethylamide of Compound 1One mole of the acid chloride of compound I is treated with diethylamine(14-6 g.; 2.0 moles) in the manner and apparatus described in theprevious example to give the N,N-diethylamide of compound I.

7 EXAMPLE 15 Preparation of the Anhydria'e of Compound I Dry pyridine(158 g.; 2.0 moles) and 1 liter of dry benzene are placed in a 2-liter,3-necked, round-bottom flask fitted with a dropping funnel, mechanicalstirrer, reflux condenser, and internal thermometer. One mole of theacid chloride of compound I, which is prepared as described in aprevious example, is added rapidly with stirring to the reactionmixture. Compound I (1 mole) is then added in portions over a period ofabout 10 minutes with rapid stirring. The pyridine hydrochloride whichprecipitates is filtered off, and the benzene 1s d1stilled from thefiltrate in vacuo. The residue contains the desired anhydride ofcompound I, which can be purified by crystallization from a suitablesolvent.

Percent Compound I 25 Antarox A-400 110 Methanol Antarox A-400 is thetrade name under which a nonionic detergent of the aromatic polyethyleneglycol ether type is sold. The above concentrate is diluted with Waterto the desired concentration for use.

EXAMPLE 17 Preparation of an Emulsifiable Concentrate of the n-ButylEster of Compound I The following ingredients are mixed thoroughly inthe given percentage proportions by weight:

Percent n-Butyl ester of compound I 59 Xylene Triton X-100 5 Kerosene 26Triton X-100 is the trade name under which an emulsifier of the alkylaryl polyether alcohol type is sold. The above concentrate is dilutedwith water to the desired concentration for use.

EXAMPLE 18 Preparation of a Dust from the Sodium Salt of Compound I Thesodium salt of compound I (10% by weight) and talc (90% by weight) arecombined and ground to the desired particle size in a mechanicalgrinder-blender.

The herbicidal activity of chemical compounds is often demonstrated bythe ability of the chemicals to kill or arrest the growth of tomatoplants. The tomato plant is readily grown and maintained under uniformconditions for experimental purposes in greenhouses, and its response tochemicals is very similar to that observed for a wide variety ofeconomically important species of undesirable plant life in the field.

The herbicidal activity of the compounds of this invention, for example,can be demonstrated in greenhouse experiments on young potted tomatoplants (Bonny Best variety). The compounds are formulated into 10percent wettable powders and are dispersed in water at a concentrationof 2,000 parts per million actual chemical. Ten milliliters of analiquot portion of the dispersion is added to the soil surface of thetomato plants, approximately 5 to 7 inches tall. In order to avoid undueconcentration or accumulation of the chemical in any given area, 5 holesthe size of a pencil and about 1 inch deep are punched in the soilsurface around the shoot, and the 10 milliliter application is dividedequally among the 5 holes. Three plants are used for each application.The treated plants are held under greenhouse conditions for 7 days,provided with subterranean watering, and observed for response totreatment. The results indicate a high order of herbicidal toxicity ofthe compounds of this invention.

This application is a division of my copending application Serial No.766,660, filed October 13, 1958, now Patent No. 3,013,056.

I claim:

1. A method of destroying growing weeds which comprises contacting saidweeds with a herbicidal composition comprising an inert carrier and asthe essential active ingredient, in a quantity which is herbicidallytoxic to said weeds, a compound selected from the group consisting of3-methoxy-2,6-dichlorophenylacetic acid, its anhydride, its alkali metalsalts, its alkyl and alkanol amine salts wherein the amine componentcontains up to ten carbon atoms, its ammonium salt, its morpholine salt,its esters wherein the esterifying group is an unsubstituted alkyl groupcontaining from one to ten carbon atoms, its alkyl amides wherein theamine component contains up to ten carbon atoms, and its unsubstitutedamide.

2. The method of claim 1, wherein the compound is an alkali metal saltof 3-methoxy-2,6-dichlorophenylacetic acid.

3. The method of claim 1, wherein the compound is an alkyl amine salt of3-methoxy-2,6-dichlorophenylacetic acid in which the amine componentcontains up to ten carbon atoms.

4. The method of claim 1, wherein the compound is an alkanol amine saltof 3-methoxy-2,6-dichlorophenylacetic acid in which the amine componentcontains up to ten carbon atoms.

5. The method of claim 1, wherein the compound is an ester of3-methoxy-2,6-dichlorophenylacetic acid in which the esterifying groupis an unsubstituted alkyl group containing from one to ten carbon atoms.

6. The method of claim 1, wherein the compound is an alkyl amide of3-methoxy-2,6-dichlorophenylacetic acid in which the amine componentcontains up to ten carbon atoms.

7. The method of claim 1, wherein the compound is3-methoxy-2,6-dichlorophenylacetic acid.

8. The method of claim 1, wherein the compound is sodium3-methoxy-2,6-dichlorophenylacetate.

9. The method of claim 1, wherein the compound is the dimethylamine saltof 3-methoxy-2,o-dichlorophenylacetic acid.

10. The method of claim 1, wherein the compound is methyl3-methoxy-2,6-dichlorophenylacetate.

11. The method of claim 1, wherein the compound isbis(3-methoxy-2,6-dichlorophenylacetic) anhydride.

12. The method of claim 1, wherein the compound is3-methoxy-2,6-dichlorophenylacetamide.

References Cited in the file of this patent UNITED STATES PATENTS2,394,916 Jones Feb. 12, 1946 2,977,212 Tischler Mar. 28, 1961

1. A METHOD OF DESTROYING GROWING WEEDS WHICH COMPRISES CONTACTING SAIDWEEDS WITH A HERBICIDAL COMPOSITION COMPRISING AN INERT CARRIER AND ASTHE ESSENTIAL ACTIVE INGREDIENT, IN A QUANTITY WHICH IS HERBICIDALLYTOXIC TO SAID WEEDS, A COMPOUND SELECTED FROM THE GROUP CONSISTING OF3-METHOXY-2-6-DICHLOROPHENYLACETIC ACID, ITS ANHYDRIDE, ITS ALKALI METALSALTS, ITS ALKYL AND ALKANOL AMINE SALTS WHEREIN THE AMINE COMPONENTCONTAINS UP TO TEN CARBON ATOMS, ITS AMMONIUM SALT, ITS MORPHOLINE SALT,ITS ESTERS WHEREIN THE ESTERIFYING GROUP IS AN UNSUBSTITUTED ALKYL GROUPCONTAINING FROM ONE TO TEN CARBON ATOMS, ITS ALKYL AMIDES WHEREIN THEAMINE COMPONENT CONTAINS UP TO TEN CABRON ATOMS, AND ITS UNSUBSTITUTEDAMIDE.